The role of high doping levels and the interfacial structure on the junction behavior between n-type silicon microwires and the conducting polymer, PEDOT:PSS, was investigated using tungsten probes, an established technique for Ohmic contact to individual microwires. The resistance and the doping density of carriers as a function of length along each microwire as well as the junction resistance between individual microwires and the conducting polymer were characterized by making Ohmic contact to microwires. The junction between highly-doped n-Si microwires and the conducting polymer had relatively symmetric current-voltage characteristics and a significantly lower junction resistance as compared to low-doped microwires. The current-voltage response of junctions formed between the polymer and low-doped microwires, which still incorporated the metal catalyst used in the growth process, was also studied. Junctions incorporating copper at the interface had similar current-voltage characteristics to those observed for the highly-doped microwire, while junctions incorporating gold exhibited significantly lower resistances